Polyester plastic compositions containing bis-phenoxy flame retardants

ABSTRACT

Plastic compositions containing polyesters and bis-phenoxy compounds having the formula   WHEREIN Z is bromine or chlorine, m and m&#39;&#39; are integers having a value of 1-5, i and i&#39;&#39; are integers having a value of 0-2, R is herein defined and A is cyano nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl or halobenzyl.

United States Patent [1 1 Anderson Sept. 23, 1975 1 POLYESTER PLASTIC COMPOSITIONS CONTAINING BIS-PIIENOXY FLAME [21] Appl. No.: 330,860

Related U.S. Application Data [63] Continuation-impart of Ser. No. 260.740, June 6.

1972, abandoned.

[52] U.S. Cl.... 260/45.9 R; 260/40 R; 260/45.75,R;

. 260/4595 G [51] Int. Cl C08g 51/60 [58] Field of Search 260/459 R,45.9 56,613 B,

260/332 R, 2.5 A1, DIG. 24; 106/15 FP [56] References Cited UNITED STATES PATENTS 3,385,819 5/1968 Gouinlock 260/4575 R 3,560,441 2/1971 Schwarcz et a1. 260/457 R 3,658,634 4/1972 Yanagi ct a1 161/403 3,717,609 2/1973 Kutner 260/4595 G Primary E.\'aminerM. .1. Welsh Attorney, Agent, or Firm-Robert M. Phipps; James J. Mullen; Robert S. Frieman [57] ABSTRACT Plastic compositions containing polyesters and bisphenoxy compounds having the formula wherein Z is bromine or chlorine, m and m are integers having a value of 15, 1' and i are integers having a value of 0-2, R is herein defined and A is cyano nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, bcnzyl or halo benzyl.

14 Claims, No Drawings POLYESTER PLASTIC COMPOSITIONS CONTAINING BIS-PHENOXY FLAME which are flame retarded. Another 'object of the present invention is to provide RETARDANTS a material for polyester plastic compositions which will I not substantially adversely effect the chemical and/or This application is a continuation-in-part of copendphysical and/or mechanical properties of said composiing application Ser. No. 260,240, filed June 6, 1972 tions. and now abandoned. The entire specification of this A further object of the present invention is to provide case, Ser. No. 260,240, is to be considered as incorpoa flame retardant which is economic'and easy to incorrated herein by reference. porate into polyester plastics without being degraded The prior art considered in conjunction with the or decomposed asaresult of blending or processing oppreparation of this application is as follows: U.S. Pat. erations. Nos. 2,130,990; 2,186,367; 2,329,033; 3,666,692; It has been found that the foregoing objects can be 3,686,320; 3,658,634; German Pat. No. 1,139,636; obtained by the incorporation of a new class of bis- German Pat. No. 2,054,522; Japanese Pat. No. (72) phenoxy compounds in polyester to subsequently pro- 14,500 as cited in Volume 77, Chemical Abstracts, colvide flame retarded compositions which exhibit outumn 153737k (1972); Chemical Abstracts, Volume standing chemical, physical and mechanical properties. 13, column 448 Chemical Abstracts, Volume 3], col- The bis-phenoxy compounds used in the present inumn 7045 and Journal of the Chemical Society, pages vention composition have the formula:

A1 A I 2972-2976 1963). All of these publications are to be In Formula I above, Z is bromine or chlorine, m and considered as incorporated herein by reference. m are integers each independently having a value of The present invention relates to plastic compositions 1 -5; i and i are integers each independently having a containing saturated or unsaturated polyesters (both value of 0-2; A is from the group, cyano (CN), nitro types herein referred to collectively as polyesters). (NO lower alkoxy (e.g. -OCH OC H lower More specifically, the present invention covers plastic alkyl (e.g. CH C H C l-l C 11 fluorine, dialkylcompositions containing polyesters and certain bisamino e.g. -N(CH N(C H phenyl (C H phenoxy Compounds (hereinafter defined) as flame rehalo-phenyl. benzyl 2C H and halo-benzyl; tardants for said plastic compositions. and R is from the group Polyester plastics (also commonly called resins) and utility thereof are known in the art as exemplified by (a) Cl-l Cl-l(OH)-CH Polyesters and Their Applications, Bjorksten Research y (b) CH2 CH(CH2OH Laboratories, Inc., Reinhold Publishing Corporation, --CH New YOrk, 1956 and Modern Plastics Encyclopedia g (CH1)-o (CH1)w 2 gig- I B 1972-1973, Vol. 49: No. 10A, October, 1972, pages j w 73, 76, 78, 79 and 156-158 and which publications are j T X in toto incorporated herein by reference.

The need for flame retarding polyesters has also been recognized in the art as exemplified by US. Pat. No. 3,347,822 and US. Pat. No. 3,422,048, and Modern Plastics Encyclopedia, ibid, pages 217, 224-229, 235 and 456-458 and which publications are in toto incorporated herein by reference. I 50,

The resultant disadvantages in the utilization of various prior art materials as flame retardants for polyesters include, without limitation, factors such as thermal migration, heat instability, light instability, non-. biodegradable, toxicity, discoloration and the large amounts employed in order to be effective. Thus, there f where 5 saturated is always a demand for a material which will function ring as a flame retardant in polyesters and concurrently will I H C CH not, by incorporation therein, adversely effect the a chemical and/or physical and/or mechanical properties of the resultant polyester plastic composition.

c11 cu;

(e) CH C(O)CH (f) CH2CH ln Formula 1, i m or i m is not greater than 5.

The prior art problem of providing a flame retarded It is to be understood that all of the compounds fallpolyester composition having desired chemical, physiingwithin the above Formula I and as heretofore decal and mechanical properties has now been substan' fined are generically described herein as bis-phenoxy tially solved by the present invention and the abovecompounds.

described disadvantages substantially overcome, The bis-phenoxy compounds are found to be compat- Accordingly, one of the main objects'of the present ible with and effective additives for various polymeric invention is to provide polyester plastic compositions systems to make the resultant polymer flame retardant.

9 Table I Co ntinued..,

Com-

No. Z m m A 1' R r 173 ci 3 3 F 2 z HZC cH 174 Br 1 1 c,11, .7 1 1 me 175 Br 1 1 -oc,H, 1 1 "inc In general, the bis-phenoxycompounds are prepared by reacting a halogenated phenol with a halogenated "alkane at elevated temperatures'in the presence of a "basic material such as alkali metal hydroxides, carbonates, bicarbonates, oxides and hydridesf The' preferred alkali metals are potassium and sodium. Where one desires to increase, for example, easeof handling the re-- action mass, solvents such as ketones (e.g. acetone, methyl ethyl ketone, and methyl isobutyl ketone), al

cohols (e.g. methanol, ethanol, iso-propyl alcohols,

butyl alcohol and glycols), or aqueous solvents (e.g.

water, a mixture of water and alcohol and a mixture'of:

water and ketone) can be employed. The desired end product i.e. the bis-phenoxy compound, can be recovered from the reaction mass via various methods such as distillation or crystallization. Where the end product requires recovery via crystallization, various aromatic solvents such as benzene, toluene, xylene, dichloroben-.

zene and the like can be used.

Specifically, the bis-phenoxy compounds are prepared according to the following-reactions:

In the above reaction, X is halogen, preferably chlo-,

rine and R is the same as defined herein, 'Where-m and m and i and i are different integers, then equivalent molar portions of the particular halogenated phenol are used with equivalent portion phenol.

ranging from the freezing point of the initial reaction mass to the boiling point thereof. Preferably the tern;

s of dissimilar halogenated The above reaction is conducted at temperatures peratures are from about 40C to aboutZOO .C and more preferably from about 50C to about l75 C. It i The above-described processes can be carried out with conventionalf'rea'dily' available chemical processirig equip'me ntQ'For example, aeonventional -glasslin'ed vessel provided with heat transfer means, a reflux con de'ns'e'r and a mechanical stirrer can be advantageously utilized in practicing any of the preferred embodiments of the invention described in the'examples set forth e-remj i The amountfof bis-phenox'y compound employed in the" present invention compositions is any quantity whiiih will effectively fender the polyester containing composition flame retardant; In general, the amount used is'fromabout jlqh to 25% by weight, based on the total Weight of the composition. Preferably, the amount employed is from about 5% 10 about 20% by weight. It is to be understood that any amount can be used as long as it does not substantially adversely effect the chemical and/or physical and/or meehanical properties of the end polymer composition. Theamount utilized, however, is suchainou nt which achievcsthe objectives described herein.

- it, is to .be understood that the term polyesters as used hereinmeans polycondensate products of the reaction of dibasicacidsand/or anhydrides or derivatives therefrom with dihy'droxy alcohols. This term'includes both saturated and unsaturated polyesters but excludes 'th'ose linear polyesters used for fibers. Unsaturated polyesters are so designated where part or all of the respective acids, anhydrides and/or .alcohols contain c'rosslinkable ethylenic bonds.

Examples of dibasic acids andanhydrides include,

without limitation, phthalic anhydride, maleic anhy-' dride, fumaric acid; tetrahydrophthalic anhydride, tet rachlorophthalic anhydride, tetrabromophthalic anhydride, l,4,5,6,7,7-hexachlorobicyclo (2,2,1 )-5- heptene-2,3-dicarboxylic acid i.e. chlorendic acid, isophthalic acid and terephthalic acid.

Examples of dihydroxy alcohols include, without limitation, ethylene glycol. diethylene glycol, propylene glycol, butane glycol, butene diol, hexane diol, hexene diol, butyne diol, cyclohexane diol, cyclohexene diol, neopentyl glycol, hydrogenated bisphenol A, 2,2,4- trimethyl-l ,3-pentanediol and IA- cyclohexanedimethanol.

This term also includes copolymers of polyesters which are resins derived from reactants used to give polyester resins and reactants used to give other polycondensate linkages. For example, there may be mentioned the reaction of dibasic anhydrides with dihydroxy alcohols and diamines to give polyester and poly amide links along the same molecular backbone. Also, those products formed by addition polymerization of reactants with ethylenic linkages before or after the polyester condensation reaction. For example, the addition reaction of styrene with unsaturation in polyesters after polycondensation or the formation of an additional polymer with carboxylic acid or other condensable end-groups for further polymerization by polyesterifi cation.

Thus the polyesters used in the present invention compositions is any polyester herein defined and which one sodesires to flame retard. It is to be understood that the polyesters used can be a "virgin" material, i.e. substantially free of additives such as stabilizers, plasti' cizers, dyes, pigments, fillers, and the like, or the polyesters can have additives (such as those mentioned and described herein) already contained therein or added concurrently with or after the addition of the bisphenoxy compounds. 7'

Another facet of the present invention relates to the use of certain metal compounds with the bis-phcnoxy compounds to promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These enhancing agents" are from the group antimony, arsenic, bismuth, tin and zinc-containing compounds. Without limitation, examples of said enhancing agents include Sb O SbCl SbBr SbI- SbOCl, As O As O ZnBO BaB O 'H O, 2-ZnO-3B O-3.5- H 0 and sta'nnous oxide hydrate. The preferred enhancing agent is antimony trioxide.

The amount of enhancing agent employed in-the present invention compositions is any amount which when used with said bis-phenoxy compounds will promote a cooperative effect therebetween. In general. the

amount employed is from about 1% to about 15 /2, pre ferably from about 2% to about 10%, by weight, based on the total weight of plastic composition. Higher amounts can be used as long as the desired end result is achieved. It is also within'the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promotors; antioxidants; antistatic agents; antimicrobials; colorants; flame retardants such as those listed on pages 456458, Modern Plastics -En- Cyclopedia, ibid. (in addition to the new class of flame retardants described herein); heat stabilizers; light stabilizers; pigments; plasticizers; preservatives; ultraviolet stabilizers and fillers.

In this latter category, i.e. fillers, there can be men' tioned without limitation, materials such as glass; carbon; cellulosic fillers (wood flour, cork and shell flour);

calcium carbonate'(clialk; limestone, and precipitated calcium carbonate); metal flakes; metallic oxides (aluminum, beryllium oxide and magnesia); metallic powders (aluminum, bronze, lead, stainless steel and zinc); polymers (comminuted polymers and elastomer-plastic bends);. silica products (diatomaceous earth, novaculite,'quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica); silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including fillers, are more fully described in Modern Plastics Encyclopedia, ibid, and which publication is incorporated herein (in toto) by reference.

The amount of the above described materials employed in the present invention compositionscanbe any quantity which will not substantially adversely;effeet the desired results derived from the present invention compositions. Thus, the amount used can be 0 percent, based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about 0% to about 75% and specifically from about 1% to about The bis-phenoxy compounds can be incorporated in to the polyesters at any processing stage in order to prepare the present invention compositions. In general, this is undertaken prior to fabrication either by physical blending or during the process of forming polyesters per se. Where one so desires, the bis-phenoxy compounds may be micronized into finely divided particles prior'to incorporation into the polyesters.

EXAMPLE I I A linear saturated polyester plastic material, (Varlox 310, a product of General Electric Company) is utilized as the base resin in order to prepare 26 formulations (plastic compositions) designated Nos. 1 26 in Table II. With the exception of formulation vNo. l (the control), the particular bis-phenoxyv (and the antimony trioxide enhanching agent where indicated) is incorporated into the plastic by adding both to a Brabender mixer (Plastic-Corder, Torque Rheometer, Model PLV-lSO, C. W. Brabender Instruments Inc., South Hackensack, N.J.). The mixer is equipped with a pair of roller type blades positioned within a head provided with heat transfer means. i

The resultant mixture is heated to about 277 C.; at this temperataur'e, it is in a molten state. The percentages by weight of each component utilized in the respective formulations are listed in Table II'. Each formulation is'discharged from the mixer and upon cool-' ing solidifies and is ground into'chips. The chips are subjected to compression molding in a'Wabash press by placing said chips between two platens, the bottom of used as a basere'sin in order to prepare 26 formulations, designated NOsi'27-52 in Table 11. The particular bis-phenoxy (and antimony trioxide where indicated) is incorporated into the unsaturated polyester by mixing with 0.1% by weight, based on the total weight of the formulation, cobalt octoate and 2.0% methyl ethyl ketone peroxide to form a liquid mixture. This mixture is poured into said depressions and cured at 100 C under slight compression by the Wabash press. Formu- Iation No. 27, without additives, is the control.

Portions of the solid samples of each respective formulation (Nos. 1-52) prepared according to the above l0 described procedures are then subjected to two different standard flammability tests, i.e. UL 94 and ASTM D-2863-70. The UL 94 is, in general, the application of a burner to a test specimen (strip) for a certain period of time and observation of combustion, burning, and

extinguishment. This procedure is fully set forth in Underwriters Laboratories bulletin entitled UL 94, Standard for Safety, First Edition, September 1972 and which is incorporated herein by reference. ASTM No. D-2863-70 is a flammability test which correlates the flammability of a plastic specimen to the available oxygen in its immediate environment; this correlation is stated as an Oxygen Index, 0.1., level predicated upon the percent oxygen in the gaseous medium which is required to just provide a steady state of continuous burning of the plastic specimen. This ASTM method is fully described in 1971 Annual Book of ASTM Standards Part 27, published by the American Society For Testing and Materials, I916 Race Street, Philadelphia, Pa; this publication is to be considered as incorporated (in toto) herein by reference.

The results of these flammability tests are shown in Table II.

TABLE II FLAMMABILITY DATA FOR POLYESTER PLASTIC COMPOSITIONS CONTAINING BISPHENOXY COMPOUNDS FORMULA- BISPHENOXY COM- ENHANCING OXYGEN TION POUND AGENT INDEX I. 0 0 22.0 SB

3. 2 20 I0 3I.5 SE2 4. I9 20 0 23.0 SB

5. I9 20 I0 30.0 SE2 9. 47 20 I0 28.5 SE-Z I0. (17 20 0 25.0 SEZ I l 67 20 I0 33.0 SEl I 83 20 0 25.0 SE2 I3 83 20 I0 33.5 SE(I I4 92 20 0 245 SB I5 92 20 I0 38.5 SE0 I6 I02 20 0 245 SB I7 I02 20 I0 33.0 SEl I8. I I9 20 0 24.0 SB l9. II9 20 I0 3I.5 SEZ 20. I27 20 0 23.5 SB 2|. I27 20 I0 325 SEl 22 I45 20 0 23.0 SB 23 I45 20 I0 29.5 SF.-2 4 I52 20 0 24.5 SB 25 I52 20 I0 34.5 SEE-0 26. 55 20 I0 35.5 SE(I 27. 0 0 I8.0 SB 28. 2 20 0 2|.5 SB 29. 2 20 I0 3L5 SE() 30. I9 20 0 20.5 SB 3 I. I9 20 10 29.0 SEO 32 33 20 0 2|.5 SB 33 33 20 I0 28.5 SE0 34 47 20 0 20.5 SB 35 47 20 I0 27.5 SE2 36 67 20 0 22.0 SB 37 67 20 I0 30 5 SE-0 38 83 20 0 23.0 SB 39. 83 20 10 31.0 SE() 40. 92 20 0 22.5 SB 4l. 92 20 10 36.5 SF.- 0 42. I02 20 0 22.5 SB 43. I02 20 I0 31.0 SE() 44. I I9 20 0 22.0 SB 45. I I9 20 [0 29.5 SEl) 46 I27 20 0 205 SB 47 I23 20 10 30.0 SE() 48 I 20 0 20.5 SB 49. I45 20 I0 28.5 SE-0 50. I52 20 0 2L5 SB 5I. I52 20 I0 3L5 SE0 52. 55 20 I0 33.0 SE(I Referring to Table II, the bisf-phenox y compound number relates to the structural formulae hjeretofor set' forth in Table I; a difference 'of2% in'theOxygen'Index values is considered significant; and the UL94 values are on a graduated scale wherein the highest degree to lowest degree of flam'e retardancy is respectively SE-O, SE-l, SE-ZQSB and Burns. 1 V v The results shown in'Table II demonstrate the unique effectiveness of these bis-'phen'o'xys as flame retardants for polyesters. With reference to the saturated polyester based formulations (Nos. -l'26') formulation No; l (the control) had a-0.l."of 22.0 and'UL 94 value of SB. The even numbered formulations, employing theuse of the particular bis-phenoxy compound "all sli'ow an increase in fire retardancy as measured by 0.1. While some formulations have a SB rating (UL 94),the individual U.L. rating covers a wide range and= consequently, in these cases, the 01. numbers are more indicative of increased flame retardancy. The use of an enhancing agent such as Sb O to promote a cooperative effect between such agent and the bis-phenoxy compounds is fully demonstrated via the results obtained from testing the odd numbered formulations. The highest UL 94 ratings and significantly higher O.I. values are obtained when using anenhancing agent.

The results obtained using an unsaturated polyester,

are basically similar to those obtained using the saturated polyester.-'Formulation Nos. 28-52 alldemonstrated a significant increase in 0.]. values as compared to the control, No. 27.

EXAMPLE II Portions of the solid samples 'of Formulation Nos. 1-52 prepared according to the above described procedure of Example I are subjected to the following ASTM tests in order to ascertain other properties of the resultant plastic composition:

Tensile Strength (at break) Flexural Strength Flexural Modulus Notched Izod Impact ASTM Test No. D638--6lT; ASTM Test N0. D79063;

: ASTM Test No. D79063;

: ASTM Test No. D256-D56; and

Heat Distortion Temperature (HDT) 1 ASTM Test No. D647-56.

Each of the aforementioned ASTM Tests are standard tests in the art and are utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retarded composition for commercial application (Formulation Nos. 27-52 are not subjected to the Izod Impact test since they are not reinforced and consequently, impact testing is not appropriate since any data obtained would not have significant meaning). All of these ASTM Tests are to be considered as incorporated herein by reference.

The results of these ASTM tests show that the physical properties of the present invention compositions are basically the same (except 0.1. and UL 94 values) as the plastic material without the flame retardant (i.e. formulation Nos. 1 and 27). Thus, there is no substantial adverse effect on the physical properties of the plastic material when the novel compounds are incorporated therein.

EXAMPLE III The procedure of Examples I and II are repeated except that the enhancing agent used is zinc borate ining an operating'temperature-of F: and a5()% rela-i tive humidity, each strip issubjected-to 200 hours "of simulated daylight-.via.:the use of a carbon arc. The

results sho'wthat after-200 hours,-there is no significant discoloration in any strip tested and which demonstrates .that' the present invention compositions. are

highly resistant to deterioration by light. h

' EXAMPLE v Samples of each of Formulation Nos. 1 through 52 Table II, are subjected to temperature (thermal) stability tests via the use of thermal gravimetric analysis (TGA). This test employed the use of a Thermal Balance, model TGS-l, Perkin-Elmer Corporation, Norwalk, Connecticut and an electrical balance, Cahn 2580 model, Cahn Instrument Company, Paramount, California. The results of these tests show that the bisphenoxy compound containing Formulations had more than adequate"s tability for melt processing and subse quent heat aging (i.e. high temperature applications) and thus demonstrating that the particular bis-phenoxy are quite compatible with the plastic material. The bisphenoxy compound stability thus aids in providing sufficient flame retardancy at the plastic decomposition temperature. This test also demonstrates that these compounds do not exhibit migration.

.In view of the foregoing Examples and remarks, it is seen that the plastic compositions, which incorporate these compounds, possess characteristics which have been unobtainable in the prior art. Thus, the use of these compounds in the above described plastic material as flame retardants therefor is quite unique since it is not possible 'to predict the effectiveness and functionality of any particular material in any polymer system until it is actively undergone incorporation therein and the resultant plastic composition tested accordingly to various ASTM Standards. Furthermore, it is necessary, inorder to have commercial utility, that the resultant flame retarded plastic composition possess characteristics such as being non-toxic. Use of these compounds in the plastic material has accomplished all of these objectives.

The above examples have been described in the foregoing specification for the purpose of illustration and not limitation.-Many other modifications and ramifications will naturally suggest themselves to those skilled in the art based on this disclosure. These are intended to be comprehended as within the scope of this invention.

. What is claimed is:

l. A plastic composition containing polyester having incorporated therein an effective amount of a flame retardant which is a compound having the formula:

wherein Z is selected from the group consisting of bromine or chlorine; m and m are integers having a value of l-5; i and i are integers having a value of 2; A is selected from the group consisting of cyano. nitro. lower alkoxy, lower alkyl, fluorine dialkylamino, phenyl, halo-phenyl, benzyl and halobenzyl; and R is selected from the group consisting of 2. The composition as set forth in claim 1 wherein i and i are both 0.

3. The composition as set forth in claim 1 wherein i and i are both I.

4. The composition as set forth in claim I wherein i and i' are both 2.

5. The composition as set forth in claim 3 wherein Z is bromine and A is cyano.

6. The composition as set forth in claim 3 wherein Z is bromine and A is nitro.

7. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkoxy.

8. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkyl.

9. The composition as set forth in claim 3 wherein Z is bromine and A is fluorine.

10. The composition as set forth in claim 3 wherein Z is bromine and A is dialkylamino.

11. The composition as set forth in claim 3 wherein Z is bromine and A is phenyl.

12. The composition as set forth in claim 3 wherein Z is bromine and A is halo-phenyl.

13. The composition as set forth in claim 3 wherein Z is bromine and A is benzyl.

14. The composition as set forth in claim 3 wherein Z is bromine and A is halo-benzyl. 

1. A PLASTIC COMPOSITION CONTAINING POLYESTER HAVING INCORPORATED THEREIN AN EFFECTIVE AMOUNT OF A FLAME RETARDANT WHICH IS A COMPOUND HAVING THE FORMULA:
 2. The composition as set forth in claim 1 wherein i and i'' are both
 0. 3. The composition as set forth in claim 1 wherein i and i'' are both
 1. 4. The composition as set forth in claim 1 wherein i and i'' are both
 2. 5. The composition as set forth in claim 3 wherein Z is bromine and A is cyano.
 6. The composition as set forth in claim 3 wherein Z is bromine and A is nitro.
 7. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkoxy.
 8. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkyl.
 9. The composition as set forth in claim 3 wherein Z is bromine and A is fluorine.
 10. The composition as set forth in claim 3 wherein Z is bromine and A is dialkylamino.
 11. The composition as set forth in claim 3 wherein Z is bromine and A is phenyl.
 12. The composition as set forth in claim 3 wherein Z is bromine and A is halo-phenyl.
 13. The composition as set forth in claim 3 wherein Z is bromine and A is benzyl.
 14. The composition as set forth in claim 3 wherein Z is bromine and A is halo-benzyl. 